CN110564092A - Preparation method and application of PMMA/graphene nano film material - Google Patents
Preparation method and application of PMMA/graphene nano film material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 115
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 115
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 92
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 238000009718 spray deposition Methods 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 12
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- 239000002341 toxic gas Substances 0.000 description 1
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Abstract
The invention discloses a preparation method and application of a PMMA/graphene nano film material, wherein 15-25 parts of self-made PMMA grafted graphene and 100 parts of PMMA are added into dichloroethane solution and uniformly stirred to form a solution solid-liquid ratio of 1.0g/L, and then the PMMA/graphene nano film is prepared by passing the solution through a multi-source spray deposition device. The PMMA/graphene nano film prepared by the method is applied to formaldehyde detection, and the sensitivity of the PMMA/graphene nano film to formaldehyde is obviously improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method and application of a PMMA/graphene nano film material.
background
formaldehyde is irritant and suffocative at normal temperature, is colorless gas, is a carcinogen, causes central nervous system injury, immune system disorder, respiratory system diseases and the like, is extremely harmful to human bodies, is one of environmental pollutants which is increasingly emphasized, and is also one of the leading causes of decoration pollution in China. In recent years, with the progress of chemical detection and analysis technology, rapid detection of formaldehyde has been rapidly developed, and formaldehyde test paper is a commonly used detection method, but the test paper has a short storage period due to easy migration of probe molecules.
surface acoustic wave Sensors (SAW) have a highly selective, highly sensitive gas sensing technology and are an important means of detecting toxic gas species. For the detection of formaldehyde, various SAW sensors have been investigated, including metal oxides such as SnO2and NiO, polymers such as polyaniline and Polyethyleneimine (PEI), composites such as PEI/TiO2And PEI/MWCNTs. Since different compounds are combined into a sensing layer, the components must not only be very compatible, but also highly sensitive to gases.
graphene is a two-dimensional carbon allotrope material, has special electronic, chemical, mechanical, thermal and optical properties, and has poor detection sensitivity due to the fact that the graphene surface does not have dangling bonds and is not easy to adsorb gas molecules. It is desirable to improve its sensitivity by some processes, for example, coating graphene with some thin polymer layers, but the nano-particles can be difficult to disperse uniformly in the polymer, and it is difficult to control the structural features such as the inter-particle distance and the surface position.
disclosure of Invention
Aiming at the technical problems that graphene is difficult to uniformly disperse and has poor compatibility with a polymer matrix in the prior art, the invention provides a preparation method and application of a PMMA/graphene nano film material.
a preparation method of a PMMA/graphene nano film material comprises the following steps:
the method comprises the following steps: modification of graphene functional groups: adding 600mg of graphite oxide dry powder into 200ml of ethanol, performing ultrasonic dispersion to obtain uniformly dispersed suspension, adding polyethylene glycol, and adding N2Refluxing for 2h under protection, and reaction temperatureAdding 200ml of a hydrazine hydrate aqueous solution with the mass concentration of 75% and 5ml of N, N-Dimethylformamide (DMF) at 140 ℃, carrying out reduction reaction for 1.5h, cooling, carrying out suction filtration, repeatedly washing with deionized water and ethanol, and drying the obtained solid product in a dynamic vacuum oven at 60 ℃ for 12h to obtain the graphene with the surface functionalized modification, wherein the use amount of the polyethylene glycol is 22 times of the weight of the graphite oxide, and the use amount of the hydrazine hydrate is 15 times of that of the graphite oxide;
Step two: preparing PMMA grafted modified graphene: ultrasonically dispersing the graphene prepared in the step one in an N, N-dimethylformamide solvent, then adding maleic anhydride grafted PMMA (polymethyl methacrylate) which is 12 times of the weight of the graphene under stirring, and introducing N at the temperature of 100 DEG C2Reacting for 4 hours; finally, carrying out suction filtration, washing the product with ethanol, and drying the obtained solid product in a vacuum oven at 70 ℃ to obtain PMMA grafted modified graphene;
Step three: preparing a PMMA/graphene nano film material: and (3) adding 15-25 parts of PMMA grafted graphene and 100 parts of PMMA into a dichloroethane solution, uniformly stirring to form a solution solid-liquid ratio of 1.0g/L, and then preparing the PMMA/graphene nano film by passing the solution through a multi-source spray deposition device.
Preferably, the grafting ratio of the maleic anhydride grafted PMMA in the second step is 1.0-1.5%.
Preferably, the distance between the nozzle tip of the multi-source spray deposition device and the substrate in the third step is kept between 10 and 15 cm.
Preferably, the nozzle spraying speed of the multi-source spraying and depositing device in the third step is 15-20 ml/min.
Preferably, the multi-source spray deposition device in the third step is kept stand for 2-4 hours at 50 ℃ after spray deposition.
An application of a PMMA/graphene nano film material, wherein the PMMA/graphene nano film is applied to formaldehyde detection.
The invention has the beneficial effects that:
1. according to the invention, the self-made PMMA grafted graphene is adopted, the compatibility of the graphene and PMMA is greatly improved, the uniform dispersion of nano graphene in PMMA is realized, an obvious three-dimensional framework structure is formed, the sensitivity of the film to formaldehyde gas is improved, when the dosage of polyethylene glycol is 22 times of the weight of graphite oxide, the dosage of hydrazine hydrate is 15 times of the dosage of graphite oxide, maleic anhydride of 12 times of the weight of the graphene is added for grafting PMMA, and the grafting rate of the maleic anhydride grafted PMMA is 1.0-1.5%, the sensitivity of the PMMA/graphene nano film to formaldehyde is obviously improved.
2. By changing the technological parameters of the multi-source spray deposition device, such as: the film with different thicknesses can be obtained by the carrier gas pressure, the distance between the nozzle and the substrate, the spraying speed of the nozzle and the deposition time, and when the film thickness is 2.2 mu m, the PMMA/graphene surface structure can adsorb gas more easily, so that better sensitivity is obtained.
Drawings
FIG. 1: top view of electron micrograph of PMMA/graphene nano thin film (example 4).
FIG. 2: an enlarged view of the electron micrograph of the PMMA/graphene nano-film (example 4).
FIG. 3: side view of electron micrograph of PMMA/graphene nano-film (example 4).
FIG. 4: sensitivity response plot of PMMA (comparative example 2), graphene (comparative example 1), PMMA/graphene nano-film (example 1) at 4.0ppm formaldehyde.
FIG. 5: sensitivity response graphs of the films of example 2, comparative example 3, comparative example 4, example 3 and example 4 at 4.0ppm formaldehyde.
FIG. 6: schematic diagram of multi-source spray deposition apparatus.
FIG. 7: sensor test equipment device schematic diagram.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting.
The film formaldehyde sensitivity data of the invention is tested by a sensor testing device, the sensor is of a delay line type, the center frequency is 69.4MHz, the sensing measurement is carried out under the static condition of a closed chamber, the temperature in the box can be set to a certain value and is monitored by a thermometer. Injecting a corresponding solution containing a certain amount of formaldehyde into the small heating plate, after uniformly mixing formaldehyde gas and indoor air, opening an indoor valve to enable the gas to be in contact with the sensor, and calculating the concentration of the formaldehyde according to the volume of the evaporated steam and the total volume of the combustion chamber. Therefore, by controlling the amount of liquid dropped on the plate, formaldehyde with a concentration of 4.0ppm can be obtained. After each measurement, the box is used as a pump to clean the sensor environment by using nitrogen flow, and fig. 7 is a schematic diagram of a sensor testing device (wherein: 1 is a mixing chamber, 2 is a heating plate, 3 is a delivery pump, 4 is a thermometer, 5 is a heater stage, 6 is a SAW sensor, 7 is a network analyzer, 8 is a valve, and 9 is a computer).
Example 1:
Step one, graphene functional group modification: adding 600mg of graphite oxide dry powder into 200ml of ethanol, performing ultrasonic dispersion to obtain uniformly dispersed suspension, adding polyethylene glycol, and adding N2Refluxing for 2h under protection, wherein the reaction temperature is 140 ℃, then adding 200ml of hydrazine hydrate aqueous solution with the mass concentration of 75% and 5ml of N, N-Dimethylformamide (DMF), carrying out reduction reaction for 1.5h, finally cooling, carrying out suction filtration, repeatedly washing with deionized water and ethanol, and drying the obtained solid product in a dynamic vacuum oven at 60 ℃ for 12h to obtain the graphene with surface functionalization modification, wherein the use amount of the polyethylene glycol is 22 times of the weight of the graphite oxide, and the use amount of the hydrazine hydrate is 15 times of that of the graphite oxide;
Step two, preparing PMMA grafted modified graphene: ultrasonically dispersing the graphene prepared in the step one in N, N-Dimethylformamide (DMF) solvent, adding maleic anhydride grafted PMMA (polymethyl methacrylate) which is 12 times of the weight of the graphene under stirring, and introducing N at the temperature of 100 DEG C2Reacting for 4 hours; finally, carrying out suction filtration, washing the product with ethanol, and drying the obtained solid product in a vacuum oven at 70 ℃ to obtain PMMA grafted modified graphene;
Step three, preparing a PMMA/graphene nano film material: and (3) adding 15 parts of PMMA grafted graphene and 100 parts of PMMA in the step two into a dichloroethane solution, uniformly stirring to form a solution solid-liquid ratio of 1.0g/L, and then preparing the PMMA/graphene nano film by passing the solution through a multi-source spray deposition device.
the grafting rate of the maleic anhydride grafted PMMA is 1.5 percent, the carrier gas of the multi-source spray deposition device in the third step is nitrogen with the pressure of 10psi, the distance between the tip of the nozzle and the matrix is kept at 10cm, the spraying speed of the nozzle is 15ml/min, and after spray deposition, the mixture is kept stand for 2 hours at the temperature of 50 ℃.
Comparative example 1:
Dissolving 115 parts of graphene in a dichloroethane solution, uniformly stirring to form a solution with a solid-to-liquid ratio of 1.0g/L, and preparing the graphene nano film by using a multi-source spray deposition device. The carrier gas of the multi-source spray deposition device is nitrogen with the pressure of 10psi, the distance between the tip of the nozzle and the substrate is kept at 10cm, the spraying speed of the nozzle is 15ml/min, and after spray deposition, the device is kept stand for 2 hours at the temperature of 50 ℃.
Comparative example 2:
Dissolving 115 parts of PMMA in dichloroethane solution, stirring uniformly to form solution with solid-to-liquid ratio of 1.0g/L, and preparing the PMMA film by using a multi-source spray deposition device. The carrier gas of the multi-source spray deposition device is nitrogen with the pressure of 10psi, the distance between the tip of the nozzle and the substrate is kept at 10cm, the spraying speed of the nozzle is 15ml/min, and after spray deposition, the device is kept stand for 2 hours at the temperature of 50 ℃.
Referring to fig. 4, from the response curves of the sensors coated with the films of example 1 and comparative examples 1 and 2 over time, it can be seen that the PMMA/graphene nano thin film sensor has superior performance to the pure graphene and PMMA sensors, the frequency shift of the PMMA/graphene nano thin film is about 6.9kHz, and the frequency shifts of the pure graphene and PMMA are 2.0 and 0.5kHz, respectively.
Example 2:
Step one, graphene functional group modification: adding 600mg of graphite oxide dry powder into 200ml of ethanol, performing ultrasonic dispersion to obtain uniformly dispersed suspension, adding polyethylene glycol, and adding N2Refluxing for 2h under protection at the reaction temperature of 140 ℃, adding 200ml of 75% hydrazine hydrate aqueous solution with mass concentration and 5ml of N, N-Dimethylformamide (DMF), carrying out reduction reaction for 1.5h, cooling, carrying out suction filtration, repeatedly washing with deionized water and ethanol, drying the obtained solid product in a dynamic vacuum oven at the temperature of 60 ℃ for 12h to obtain the graphene with surface functionalization modification, wherein polyethylene glycol is usedThe amount of the hydrazine hydrate is 22 times of the weight of the graphite oxide, and the amount of the hydrazine hydrate is 15 times of that of the graphite oxide;
Step two, preparing PMMA grafted modified graphene: ultrasonically dispersing the graphene prepared in the step one in N, N-Dimethylformamide (DMF) solvent, adding maleic anhydride grafted PMMA (polymethyl methacrylate) which is 12 times of the weight of the graphene under stirring, and introducing N at the temperature of 100 DEG C2Reacting for 4 hours; finally, carrying out suction filtration, washing the product with ethanol, and drying the obtained solid product in a vacuum oven at 70 ℃ to obtain PMMA grafted modified graphene;
step three, preparing a PMMA/graphene nano film material: and (3) adding 15 parts of PMMA grafted graphene and 100 parts of PMMA in the step two into a dichloroethane solution, uniformly stirring to form a solution solid-liquid ratio of 1.0g/L, and then preparing the PMMA/graphene nano film by passing the solution through a multi-source spray deposition device.
The grafting rate of the maleic anhydride grafted PMMA is 1.0 percent, the carrier gas of the multi-source spray deposition device in the third step is nitrogen with the pressure of 15psi, the distance between the tip of the nozzle and the matrix is kept at 10cm, the spraying speed of the nozzle is 20ml/min, and after spray deposition, the mixture is kept stand for 4 hours at the temperature of 50 ℃. The thickness of the film prepared under this combination and process conditions was 2.8 microns.
comparative example 3:
Step one, graphene functional group modification: adding 600mg of graphite oxide dry powder into 200ml of ethanol, performing ultrasonic dispersion to obtain uniformly dispersed suspension, adding polyethylene glycol, and adding N2Refluxing for 2h under protection, wherein the reaction temperature is 140 ℃, then adding 200ml of hydrazine hydrate aqueous solution with the mass concentration of 75% and 5ml of N, N-Dimethylformamide (DMF), carrying out reduction reaction for 1.5h, finally cooling, carrying out suction filtration, repeatedly washing with deionized water and ethanol, and drying the obtained solid product in a dynamic vacuum oven at 60 ℃ for 12h to obtain the graphene with surface functionalization modification, wherein the use amount of the polyethylene glycol is 20 times of the weight of the graphite oxide, and the use amount of the hydrazine hydrate is 11 times of that of the graphite oxide;
Step two, preparing PMMA grafted modified graphene: ultrasonically dispersing the graphene prepared in the step one in N, N-Dimethylformamide (DMF) solvent, and then adding graphite under stirring10 times of the weight of the olefin, maleic anhydride grafted PMMA, N was fed at a temperature of 100 DEG2Reacting for 4 hours; finally, carrying out suction filtration, washing the product with ethanol, and drying the obtained solid product in a vacuum oven at 70 ℃ to obtain PMMA grafted modified graphene;
Step three, preparing a PMMA/graphene nano film material: and (3) adding 15 parts of PMMA grafted graphene and 100 parts of PMMA in the step two into a dichloroethane solution, uniformly stirring to form a solution solid-liquid ratio of 1.0g/L, and then preparing the PMMA/graphene nano film by passing the solution through a multi-source spray deposition device.
the grafting rate of the maleic anhydride grafted PMMA is 0.8 percent, the carrier gas of the multi-source spray deposition device in the third step is nitrogen with the pressure of 15psi, the distance between the tip of the nozzle and the matrix is kept at 10cm, the spraying speed of the nozzle is 20ml/min, and after spray deposition, the mixture is kept stand for 4 hours at the temperature of 50 ℃. The thickness of the film prepared under this combination and process conditions was 2.8 microns.
comparative example 4:
Step one, graphene functional group modification: adding 600mg of graphite oxide dry powder into 200ml of ethanol, performing ultrasonic dispersion to obtain uniformly dispersed suspension, adding polyethylene glycol, and adding N2Refluxing for 2h under protection, wherein the reaction temperature is 140 ℃, then adding 200ml of hydrazine hydrate aqueous solution with the mass concentration of 75% and 5ml of N, N-Dimethylformamide (DMF), carrying out reduction reaction for 1.5h, finally cooling, carrying out suction filtration, repeatedly washing with deionized water and ethanol, and drying the obtained solid product in a dynamic vacuum oven at 60 ℃ for 12h to obtain the graphene with surface functionalization modification, wherein the use amount of the polyethylene glycol is 22 times of the weight of the graphite oxide, and the use amount of the hydrazine hydrate is 15 times of that of the graphite oxide;
step two, preparing PMMA grafted modified graphene: ultrasonically dispersing the graphene prepared in the step one in N, N-Dimethylformamide (DMF) solvent, adding maleic anhydride grafted PMMA (polymethyl methacrylate) which is 12 times of the weight of the graphene under stirring, and introducing N at the temperature of 100 DEG C2Reacting for 4 hours; finally, carrying out suction filtration, washing the product with ethanol, and drying the obtained solid product in a vacuum oven at 70 ℃ to obtain PMMA grafted modified graphene;
step three, preparing a PMMA/graphene nano film material: and (3) adding 15 parts of PMMA grafted graphene and 100 parts of PMMA in the step two into a dichloroethane solution, uniformly stirring to form a solution solid-liquid ratio of 1.0g/L, and then preparing the PMMA/graphene nano film by passing the solution through a multi-source spray deposition device.
the grafting ratio of the maleic anhydride grafted PMMA is 1.8 percent, the carrier gas of the multi-source spray deposition device is nitrogen with the pressure of 9psi, the distance between the tip of a nozzle and the matrix is kept at 17cm, the spraying speed of the nozzle is 12ml/min, and after spray deposition, the mixture is kept stand for 1.5 hours at the temperature of 50 ℃. The thickness of the film prepared under this combination and process conditions was 0.6 microns.
Example 3:
Step one, graphene functional group modification: adding 600mg of graphite oxide dry powder into 200ml of ethanol, performing ultrasonic dispersion to obtain uniformly dispersed suspension, adding polyethylene glycol, and adding N2Refluxing for 2h under protection, wherein the reaction temperature is 140 ℃, then adding 200ml of hydrazine hydrate aqueous solution with the mass concentration of 75% and 5ml of N, N-Dimethylformamide (DMF), carrying out reduction reaction for 1.5h, finally cooling, carrying out suction filtration, repeatedly washing with deionized water and ethanol, and drying the obtained solid product in a dynamic vacuum oven at 60 ℃ for 12h to obtain the graphene with surface functionalization modification, wherein the use amount of the polyethylene glycol is 22 times of the weight of the graphite oxide, and the use amount of the hydrazine hydrate is 15 times of that of the graphite oxide;
Step two, preparing PMMA grafted modified graphene: ultrasonically dispersing the graphene prepared in the step one in N, N-Dimethylformamide (DMF) solvent, adding maleic anhydride grafted PMMA (polymethyl methacrylate) which is 12 times of the weight of the graphene under stirring, and introducing N at the temperature of 100 DEG C2reacting for 4 hours; finally, carrying out suction filtration, washing the product with ethanol, and drying the obtained solid product in a vacuum oven at 70 ℃ to obtain PMMA grafted modified graphene;
Step three, preparing a PMMA/graphene nano film material: and (3) adding 25 parts of PMMA grafted graphene and 100 parts of PMMA in the step two into a dichloroethane solution, uniformly stirring to form a solution solid-liquid ratio of 1.0g/L, and then preparing the PMMA/graphene nano film by passing the solution through a multi-source spray deposition device.
The grafting rate of the maleic anhydride grafted PMMA is 1.0 percent, the carrier gas of the multi-source spray deposition device in the third step is nitrogen with the pressure of 12psi, the distance between the tip of the nozzle and the substrate is kept at 12cm, the spraying speed of the nozzle is 18ml/min, and after spray deposition, the mixture is kept stand for 3 hours at the temperature of 50 ℃. The thickness of the film prepared under this combination and process conditions was 1.4 microns.
example 4:
Step one, graphene functional group modification: adding 600mg of graphite oxide dry powder into 200ml of ethanol, performing ultrasonic dispersion to obtain uniformly dispersed suspension, adding polyethylene glycol, and adding N2Refluxing for 2h under protection, wherein the reaction temperature is 140 ℃, then adding 200ml of a hydrazine hydrate aqueous solution with the mass concentration of 75% and 5ml of N, N-Dimethylformamide (DMF), carrying out reduction reaction for 1.5h, finally cooling, carrying out suction filtration, repeatedly washing with deionized water and ethanol, and drying the obtained solid product in a dynamic vacuum oven at 60 ℃ for 12h to obtain the graphene with surface functionalization modification, wherein the use amount of the polyethylene glycol is 22 times of the weight of the graphite oxide, and the use amount of the hydrazine hydrate is 15 times of that of the graphite oxide;
Step two, preparing PMMA grafted modified graphene: ultrasonically dispersing the graphene prepared in the step one in N, N-Dimethylformamide (DMF) solvent, adding maleic anhydride grafted PMMA (polymethyl methacrylate) which is 12 times of the weight of the graphene under stirring, and introducing N at the temperature of 100 DEG C2reacting for 4 hours; finally, carrying out suction filtration, washing the product with ethanol, and drying the obtained solid product in a vacuum oven at 70 ℃ to obtain PMMA grafted modified graphene;
Step three, preparing a PMMA/graphene nano film material: and (3) adding 20 parts of PMMA grafted graphene and 100 parts of PMMA into a dichloroethane solution, uniformly stirring to form a solution solid-liquid ratio of 1.0g/L, and then preparing the PMMA/graphene nano film by passing the solution through a multi-source spray deposition device.
The grafting rate of the maleic anhydride grafted PMMA is 1.0 percent, the carrier gas of the multi-source spray deposition device in the third step is nitrogen with the pressure of 12psi, the distance between the tip of the nozzle and the matrix is kept at 12cm, the spraying speed of the nozzle is 15ml/min, and after spray deposition, the mixture is kept stand for 3 hours at the temperature of 50 ℃. The thickness of the film prepared under this combination and process conditions was 2.2 microns.
referring to fig. 5: wherein:
Example 2:2.8 μm comparative example 3:2.8um|
comparative example 4: - ■ -0.6 μm example 3: - ● -1.4 μm
Example 4: -. solidup-2.2 μm
The film thicknesses prepared in the example 2 and the comparative example 3 are both 2.8 micrometers, and it can be seen from fig. 5 that when the amount of the polyethylene glycol is 22 times of the weight of the graphite oxide, the amount of the hydrazine hydrate is 15 times of the amount of the graphite oxide, and the maleic anhydride grafted PMMA, which is 12 times of the weight of the graphene, is added, and the grafting ratio of the maleic anhydride grafted PMMA is 1.0-1.5%, the sensitivity of the PMMA/graphene nano film to formaldehyde is obviously improved; the film thicknesses of example 2, comparative example 4, example 3 and example 4 were 2.8 microns, 0.6 microns, 1.4 microns and 2.2 microns, respectively, and it can be seen from FIG. 4 that the film thickness of 2.2 microns is optimal and the sensitivity is reduced when the film is too thick or too thin.
As can be seen from fig. 1 to 3, the thin film is smooth and dense as seen in fig. 1 (labeled a), fig. 2 (labeled b) clearly shows that the graphene/PMMA thin film is deposited by the multi-source spray deposition method, the graphene is uniformly dispersed in the PMMA matrix and forms a three-dimensional skeleton structure, and fig. 3 (labeled c) shows that the thickness of the thin film is about 2.2 μm.
Claims (7)
1. A preparation method of PMMA/graphene nano film material is characterized by comprising the following steps: the method comprises the following steps:
Firstly, modifying a graphene functional group: adding 600mg of graphite oxide dry powder into 200ml of ethanol, performing ultrasonic dispersion to obtain uniformly dispersed suspension, adding polyethylene glycol, and adding N2Refluxing for 2h under protection at 140 deg.C, adding 200ml of 75% hydrazine hydrate aqueous solution and 5ml of N, N-dimethylformamide, performing reduction reaction for 1.5h, cooling, vacuum filtering, and removingwashing the seed water and ethanol repeatedly, and drying the obtained solid product in a dynamic vacuum oven at 60 ℃ for 12h to obtain graphene with surface functionalization modification, wherein the dosage of the polyethylene glycol is 22 times of the weight of the graphite oxide, and the dosage of the hydrazine hydrate is 15 times of the dosage of the graphite oxide;
step two, preparing PMMA grafted modified graphene: ultrasonically dispersing the graphene prepared in the step one in an N, N-dimethylformamide solvent, then adding maleic anhydride grafted PMMA (polymethyl methacrylate) which is 12 times of the weight of the graphene under stirring, and introducing N at the temperature of 100 DEG C2Reacting for 4 hours; finally, carrying out suction filtration, washing the product with ethanol, and drying the obtained solid product in a vacuum oven at 70 ℃ to obtain PMMA grafted modified graphene;
Step three, preparing a PMMA/graphene nano film material: and (3) adding 15-25 parts of PMMA grafted graphene and 100 parts of PMMA into a dichloroethane solution, uniformly stirring to form a solution solid-liquid ratio of 1.0g/L, and then preparing the PMMA/graphene nano film by passing the solution through a multi-source spray deposition device.
2. The preparation method of PMMA/graphene nano film material of claim 1, which is characterized in that: and in the second step, the grafting rate of the maleic anhydride grafted PMMA is 1.0-1.5%.
3. The preparation method of PMMA/graphene nano film material of claim 1, which is characterized in that: and in the third step, the carrier gas of the multi-source spray deposition device is nitrogen with the pressure of 10-15 psi.
4. the preparation method of PMMA/graphene nano film material of claim 1, which is characterized in that: in the third step, the distance between the nozzle tip of the multi-source spray deposition device and the substrate is kept between 10 and 15 cm.
5. the preparation method of PMMA/graphene nano film material of claim 1, which is characterized in that: in the third step, the spray rate of the nozzle of the multi-source spray deposition device is 15-20 ml/min.
6. The preparation method of PMMA/graphene nano film material of claim 1, which is characterized in that: and in the third step, the multi-source spray deposition device stands for 2 to 4 hours at the temperature of 50 ℃ after spray deposition.
7. the application of the PMMA/graphene nano film material is characterized in that: the PMMA/graphene nano film is applied to formaldehyde detection.
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